LU85394A1 - WHITENING COMPOSITION COMPRISING A PERFUME-CONTAINING MEDIUM - Google Patents

Description

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The present invention relates to carriers containing a perfume which considerably improve the substantivity of perfumes with regard to washed fabrics. More particularly, the present invention relates to detergent compositions in particles which contain, as one of their components, a support containing a by smoke, which can impart a pleasant odor to the finished washed fabrics with only small quantities of perfume.

Perfumes which modify or enhance the aroma of detergent compositions or impart to them a pleasant odor are well known in the art. U.S. Patents 4,131,555 and 4,228,025 are representative of patents describing substances intended to impart a pleasant odor to liquid or granular detergent compositions. The methods of preparation described consist in mixing the perfumed substances, in solid form, with the detergent compositions prepared to form a homogeneous composition. Perfumes which are in liquid form are commonly added to liquid detergent compositions as one of their components or sprayed onto the surface of granular detergent compositions. However, the detergent compositions thus prepared cannot impart an odor to the washed fabrics despite the improved flavor of the composition itself. This is mainly due to the fact that the scent substances contained in the detergent composition are rapidly dispersed and diluted during laundering in the aqueous washing solution together with the water-soluble components of the detergent composition. As a result, only a relatively small amount of perfume remains in contact with and adheres to the fabric being washed, most of the perfume being removed from the washing machine with the washing solution during the washing cycle . In addition, since part of the perfume is still in contact with the fabric after washing, it tends to dissipate afterwards during drying, for example in a gas dryer or electric in which the washed fabrics are subjected to shaking at relatively high temperatures. Consequently, the fabrics washed with conventional detergent compositions retain only a very weak odor of perfume, which has no particular attraction for the user. There is therefore a need in practice for an additive to conventional detergent compositions which can effectively provide a scent to the washed fabrics so that the finished washed fabrics are of increased appeal to the user.

US Patent No. 4,259,373 describes an article for the treatment of fabrics for use in a washing machine or an automatic dryer consisting of a waterproof water-resistant sachet containing what is described as a sleep conditioner composition / antistatic agent. In Example II of the patent in question, a procedure is described for preparing this antistatic composition in which clay and a solid perfume are mixed and the mixture is then kneaded with atomized particles of certain salts of quaternary ammonium. The resulting composition is then introduced into a waterproof polyester bag.

The present invention provides a particulate detergent composition for laundry comprising: (a) about 0.1 to about 50% by weight of a carrier containing a perfume containing (i) separate particles comprising at least 75% by weight weight of a mineral clay other than talc and / or a zeolite, and less than about 5% by weight of surfactant detergent compounds; and (ii) a perfume, said perfume being adsorbed and / or absorbed on the particles; (b) approximately 2 to approximately 50% by weight, in addition to 3 ^ any detergent compound contained in said particles, of one or more detergent surfactant compounds chosen from anionic, nonionic detergents, cationic, ampholytic and zwitterionic; (C) about 0 to 70% by weight of a detergency builder salt, the remainder consisting of water and optionally a filler salt.

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According to another embodiment of the invention, there is provided a support containing a perfume to be used in mixture with a detergent composition in particles for laundry comprising (a) separate particles containing at least 75% by weight of (1 ) an inorganic clay other than talc and / or (2) a zeolite, and less than about 5% by weight of surfactant detergent compounds; and (b) a perfume, which perfume is in the liquid state at room temperature and is adsorbed and / or absorbed on said particles.

According to the process of the invention, the deposition of perfume on the washed fabrics is carried out by bringing the stained and / or soiled materials to be washed into contact with an aqueous solution or dispersion which contains the supports comprising a perfume as defined. above.

The term "perfume" as used herein refers to odorous materials which can impart pleasant odor to fabrics, and includes conventional materials commonly used in detergent compositions to substitute for a bad odor. these compositions and / or give them a pleasant odor *. The perfumes are preferably in the liquid state at room temperature, although solid perfumes are also of interest. The perfumes contemplated for use herein include materials such as aldehydes, ketones, esters, etc. which are commonly used to impart a pleasant odor to liquid and granular detergent compositions.

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4 of plant and animal origin are also commonly used as components of perfumes. Accordingly, the scents useful in the present invention may have relatively simple compositions or may comprise complex mixtures of natural and synthetic chemical components, all of which are intended to provide a pleasant odor when applied to fabrics. The perfumes used in the detergent compositions are generally chosen to satisfy requirements of odor, stability, price and commercial availability. A description of the materials commonly used in perfumery for detergents is given by R.T. Steltenkamp,

The Journal of The American Oil Chemists Society, Vο1.45, N ° 6, pages 429-432.

The term "particles" as used herein and in the claims with respect to the carrier containing a perfume is intended to encompass a wide variety of particulate matter in shape, chemical composition, particular dimensions. * 20 res and of different physical characteristics, the essential common characteristic being that these particles contain at least 75% by weight of a mineral clay and / or a zeolite. The particles are advantageously of a fluid nature or flowing freely. The "percentage by weight" of the mineral clay and the zeolite designates the weight of these materials including water and impurities - --------------— t associated with the clay or particular zeolite used. Therefore, the carrier particles can be in the form of finely divided powders, as well as granules, beads or agglomerated particles of *. relatively larger in size and can be produced by various manufacturing processes such as spray drying, dry mixing or agglomeration of the individual components. Particularly preferred carrier particles for use here are agglomerates 5

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of bentonite produced by the process described in patent application in France No. 8,305,622 of April 6, 1983.

The carrier particles can therefore optionally contain, in addition to mineral clay and / or zeolite, materials which are compatible with conventional bleaching compositions, examples of suitable materials including binders or agglomerating agents, for example example sodium silicate, dispersing agents, detergency builder salts as well as common secondary ingredients present in conventional laundry detergent compositions, for example dyes, optical brightening agents, anti-redeposition agents, etc. For the purposes of the present invention, the particles should contain less than about 5% by weight of surfactant detergent compounds, preferably less than about 3% by weight, and more preferably, they do not contain any at all. .

The term "distinct" as used with regard to the particles means that these particles are used in the present invention in the form of individually distinct particles, which therefore excludes, for example, the particles carrier materials included in a matrix of other materials, or which are mixed with other ingredients, so that the particles form a component of a coarser aggregate rather than being in the form of individual particles and separate.

The present invention is characterized by a carrier containing an effective perfume in which the particles contain at least 75% by weight, preferably at least 90% by weight of a mineral clay and / or a zeolite. Most of the perfume associated with the support, preferably at least 95% of it, is adsorbed and / or absorbed on the particles, the terms "adsorbed" and "ab- ........... .............................! "* 6 sique of the perfume with the particles of support. Contrary to the traditional practice in which the perfumes added to the granular detergent compositions are atomized on spray-dried water-soluble granular powders, or otherwise brought into contact with these powders, the perfumes used in the present invention come into contact with particles of a mineral clay or zeolite which are, for the most part, insoluble in water. It has been found that the perfume thus associated with the support particles remains mainly concentrated on these particles during leaching instead of being dispersed in the aqueous washing solution. offers an important advantage during the leaching operation in that the support particles contained The scent of the washing solution comes into contact with the washed fabrics and can be dispersed over these fabrics, in particular in a washing machine in which the washing solution is mechanically entrained by the fabric during the washing cycle. The perfume is thus kept close to the finished washed fabric, preventing the dissipation of the perfume from these fabrics.

The supports of 1. ' The invention containing a fragrance are intended to be used in admixture with detergent particulate compositions for bleaching operations. As a variant, the supports can advantageously be added to the washing solution separately from the detergent composition, for example during the rinsing cycle of a washing machine. The supports are formed. of two essential ingredients: a mineral clay and / or a zeolite, and a perfume. The weight ratio of mineral clay or zeolite to perfume in the carriers is generally between about 10: 1 and about 200: 1, and preferably between about 20: 1 and about 100: 1.

The weight of perfume in the medium generally varies in

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I * 7 0.5 to 5% by weight. The carriers can conveniently be used during household laundering as additives to a washing bath which contains a conventional detergent composition, as one of its constituents. These fully formulated detergent compositions generally contain (a) about 0.1 to about 50% by weight, preferably about 5 to about 30% by weight, of said carrier containing a perfume; and (b) about 2 to about 50% by weight, preferably about 5 to about 40% by weight, and more preferably about 5 to about 30% by weight of a surfactant chosen from anionic detergents, non-ionic, cationic, ampholytic and zwitterionic. The detergent compositions also optionally contain from 0 to about 70% by weight of a detergency builder salt, a concentration of about 5 to about 50% being particularly preferred. The rest of the composition contains predominantly water, filler salts such as sodium sulphate, and optionally minor components such as binders, optical brightening agents, pigments, dyes, etc., which are conventional additives for detergent formulations.

For the sake of economy, it is preferable that the major part, and in most cases, preferably · 25], has almost all of the perfume contained in the detergent composition is supplied by the supports. However, the detergent compositions useful herein may also contain perfumes in addition to that used in conjunction with the carriers described above to impart a pleasant odor to the wash solution or the composition itself. The use of other perfumes can be advantageous in cases where it is carried out in conjunction with a limited amount of a more expensive perfume. Thus, for example, it may be more advantageous from the economic point of view to use a minor quantity of a relatively expensive perfume with the support of the invention and to incorporate relatively small quantities. more important of a less expensive perfume to the granular detergent composition in the form of an additional perfume, the latter perfume being added by techniques known in the art, for example by atomization of the granular detergent powder.

*

The mineral clays which are generally useful here include a wide variety of materials among which may be mentioned clays of the smectite type; kaolinite, meta-kaolin; and attapulgite. Among the aforementioned types of clays, those of the smectite type are preferred since they exert advantageous softening effects on the washed fabrics in addition to their role of supporting the perfume according to the invention. A detailed description of the various types of clays which can all be used in the present invention is given by B. K. G. Theng, The Chemistry of Clay Organic Reacti ons, John Wiley & Sons, (1 974), pages 1-15.

The crystalline types of zeolite which can be

used here include those described in "Zeolite Mole-cular Sériés" by Donald W. Breck, published in 1974 by John Wiley & Sons, typical examples of commercially available zeolites being listed in Table 9.6 on pages 25-747-749 of the text . Type A zeolitic structures

are particularly interesting and are widely described in practice; see, for example, page 133 of the above-mentioned Breck text as well as U.S. Patent No. 2,882,243.

The zeolite of type 4A is advantageously used, the monovalent ca-tion of this zeolite being sodium and the pore size of the zeolite being approximately 0.4 nm.

The above-mentioned smectite-type clays are three-layer clays characterized by the ability of the laminated structure to increase by several times its volume by swelling or expansion when it.

9 is in the presence of water, forming a thixotropic gelatinous substance. There are two classes of smectite clays: in the first class, aluminum oxide is present in the network of crystalline silicates; 5 in the second class, magnesium oxide is present in the network of crystalline silicates. Substitution of atoms by iron, magnesium, sodium, potassium, calcium, etc., can appear in the crystal lattice of smectite-type clays. It is common practice to distinguish between clays on the basis of their predominant cation. For example, a sodium clay is a clay in which the cation is predominantly sodium. As far as the supports of the invention are concerned, α-luminium silicates in which sodium is the predominant cation, for example bentonite-type clays. Among the clays of the bentonite type, particular preference is given to those coming from Wyoming (generally designated by bentonite from the West of the United States or bentonite from Wyo-20 ming).

The preferred swelling bentonites are sold under the trademark Minerai Colloid, as industrial bentonites, by Benton Clay Company, a subsidiary of Georgia Kaolin Co. These materials which are the same as those previously sold under the trademark THIXO- JEL, are selectively extracted and enriched bentonites, and those considered to be the most useful are available under the designations Ore Colloid N ° 101, etc., corresponding to THIXO-JEL 30 N ° 1, 2, 3 and 4. These materials have a pH (concentration of 6% in water) of 8 to 9.4, maximum free moisture contents of around 8% and densities of around 2.6, and for pulverulent quality at least 85% ( and preferably 100%) pass through a 0.074mm mesh screen. More preferably, the bentonite is a bentonite in which essentially all of the particles (i.e. at least 90% of them, more preferably more than 95%) pass through a 0.044 mm mesh screen and most advantageously, all of the particles pass through this screen. The swelling power of bentonites in water is generally between 3 and 15 ml / g, and their viscosity, at a concentration of 6% in water, is generally around 8 to 30 mPa.s.

In a particularly preferred form of the invention, the carrier particles comprise agglomerates of finely divided bentonite, of particle sizes less than 0.074 mm, agglomerated into particles of dimensions essentially between 0.149 and 2.00 mm, d an apparent density of 0.7 to 0.9 g / ml and a moisture content of 8 to 13%. These agglomerates comprise approximately 1 to 5% of a binder or agglomeration agent to promote the maintenance of the integrity of the agglomerates until they are added to the water in which they are intended to disintegrate and become disper-20 ser. A detailed description of the process for the preparation of these agglomerates can be found in French patent application No. 8,305,622 of April 6, 1983.

Instead of using THIX0-JEL or the Colloid Ore bentonites, products such as those sold by the American Colloid Company, Industrial Division, under the designation "General Purpose Powder Bentonite" can be used. Bentonite Powder)., With a particle size of 0.044 mm of which a minimum of 95% is less than 44 micrometers in diameter (particle size in the wet state) and a minimum of 96% are less than 74 micrometers in diameter (dry particle size). This hydrated aluminum silicate consists mainly of montmori11 onite (90% minimum) with smaller proportions of feldspar, biotite and selenite. A typical analysis, on an "anhydrous" basis, is 63.0% i 11 of silica, 21.5% of alumina, 3.3% of ferric iron (in Fe ^^), 0.4% of ferrous iron ( in FeO), 2.7% magnesium in MgO), 2.6% sodium and potassium (in Na20), 0.7% calcium (in CaO), 5.6% water of crystallization (in 5 H ^ O) and 0.7% of elements in the form of traces.

Although bentonites from the western United States are preferable, it is also possible to use other bentonites such as those which can be obtained by processing Italian or analogous bentonites containing relatively small proportions of metals exchangeable monovalents (sodium and potassium) with alkaline materials, for example sodium carbonate, in order to increase the cation exchange capacities of these products. It is believed that the Na20 content of the bentonite should be at least about 0.5%, preferably at least 1%, and more preferably at least 2%, so that the clay swells satisfactorily, and has good softening and dispersion properties in aqueous suspension. Preferred swelling bentonites of the types described above are sold under the trademarks Lavïosa and Winkelmann, for example Laviosa AGB and Winkelmann G-13.

The supports containing a perfume according to the invention are prepared by methods which ensure the contact of almost all of the perfume with the support particles described above and its adsorption and / or absorption by these particles. A preferred technique is to spray the perfume onto the surface of the carrier particles. This can be done by atomizing the perfume from a pressure nozzle, so as to produce droplets which come into contact with the surface of the particles, the latter being conveniently on a moving belt, for example a conveyor belt . Alternatively, the method may conveniently be carried out by atomizing the perfume on the particles contained in a drum or rotary tube inclined at a slight angle, for example from about 5 ° to 15 °, the speed of rotation of this drum or tube advantageously being about 5 to 100 rpm. The appropriate size range of droplets for effective atomization can vary between about 10 and about 200 micrometers in diameter, but preferably this dimension is as small as possible relative to the diameter of the sprayed particles.

As mentioned above, the detergent compositions for the laundry according to the invention comprise a support containing a perfume as described here in combination with one or more surface-active agents chosen from anionic, nonionic or cationic detergents , am-pholytics and zwitterionics.

Among the anionic surfactants useful in the present invention, mention may be made of surfactant compounds which contain an organic hydrophobic group containing about 8 to 26 carbon atoms, and preferably about 10 to 18 carbon atoms in their form. molecular structure, and at least one water solubilization group selected from sulfonate, sulfate, carboxylate, phosphonate and phosphate so as to form a water-soluble detergent.

Examples of suitable anionic detergents include soaps such as water soluble salts (e.g. sodium, potassium, ammonium and alkanolammonium salts) of higher fatty acids or resin salts containing from about 8 to 20 carbon atoms and preferably 10 to 18 carbon atoms. ' Suitable fatty acids can be obtained from oils and waxes of animal or vegetable origin, for example tallow, fat, coconut oil and mixtures thereof. Of particular interest are the sodium and potassium salts of mixtures of fatty acids derived from co-prah oil and tallow, for example coconut sodium soap and ^ 13

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tallow potassium soap.

The anionic class of detergents also includes sulfated detergents and water-soluble sulfones having an aliphatic radical, preferably an alkyl radical containing from about 8 to 26, and preferably 12 to 22 carbon atoms. (The term "alkyl" denotes the alkyl portion of the higher acyl radicals). Examples of the sulfonated anionic detergents are the (higher alkyl) su! monocyclic aromatic fonates such as 10 (higher alkyl) benzene sulfonates containing about 10 to 16 carbon atoms in the straight or branched chain higher alkyl group, for example the sodium, potassium and ammonium salts of (higher alkyl ) benzene sulfonates, of (higher alkyl) tuuene-sulfona-15 tes and of (higher alkyl Jphenol-sulfonates.

Other suitable anionic detergents are olefin sulfonates including long chain alkene sulfonates, long chain hydroxyalkane sulfonates or mixtures of alkene sulfonates and hydroxyalkane sulfonates. Detergent olefin sulfonates can be prepared in a conventional manner by the reaction of SOg with long chain olefins containing about 8 to 25, and preferably 12 to 21 carbon atoms, for example olefins of formula RCH = CHR- where R is an upper alkyl group of about 6 to 23 carbon atoms and R. | is an alkyl group containing about 1 to 17 carbon atoms, or hydrogen to form a mixture of sultones and alcene-sulfonic acids which is then processed to convert the sultones to sulfonates. Other examples of detergent sulfates or sulfonates are paraffin sulfonates containing about 10 to 20 atoms.

carbon, and preferably about 15 to 20 carbon atoms. The primary paraffin sulfonates are obtained by the reaction of long chain alpha-olefins and de-bisulfi-

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14 distributed along the paraffinic chain are indicated in U.S. Patent Nos. 2,503,280; No. 2,507,088; No. 3,260,741; No. 3,372,188 and German Patent No. 735,096.

Other suitable anionic detergents are the ethoxylated sulfated higher fatty alcohols of formula, RO ^ H ^ O ^ SO- ^ M in which R is a fatty alkyl group of 10 to 18 carbon atoms, .m is 2- 6 (preferably a value equal to 1/5 to 1/2 the number of carbon atoms of R) and M is a forming group of solubilization salt, for example an alkali metal cation, ammonium, (lower alky1) -amino or (lower alkanol) friend -no, or a (higher alkyl) -benzene sulfonate in which the upper alkyl group contains from 10 to 15 carbon atoms. The proportion of ethylene oxide in the polyethoxylated (higher alkanol) sulfate is preferably from 2 to 5 moles of ethylene oxide groups per mole of anionic detergent, the amount of three moles being preferred, in particular when 1 ' higher alkanol has 11 to 20 carbon atoms. To maintain the hydrophilic ratio-

lipophilic desired, when the carbon atom content of the alkyl chain is in the lower portion of the range of 10-18 carbon atoms, the ethylene oxide content of the detergent can be reduced to about two moles per mole , while when the higher alkanol has 16 to 18 carbon atoms and is in the upper part of the range, the number of ethylene oxide groups can be increased to 4 or 5 and, in some cases, up to 8 or 9. Similarly, the salt-forming cation can be modified to obtain the best solubility. It may be any metal or suitable solubilization radical, but most often an alkali metal, for example sodium, or ammonium. If lower alkylamine or alkanolamine groups are used, the alkyl and alkanol groups generally contain from 1 to L

15 4 carbon atoms and the amines and alkanolami born can be mono-, di- and tri-substituted, as in the case of monoethanol amine, diisopropanolamine and trimethylami ne. A preferred polyoxyethylene detergent coolant is available from Shell Chemical Company and is marketed under the designation Neodol 25-3S.

The water-soluble anionic detergent compounds which are particularly preferred are the ammonium and substituted ammonium salts (for example of mono-, di- and trië-thanolami ne), of alkali metal (for example sodium and potassium ) and of alkaline earth metal (for example calcium and magnesium) of (higher alkyl) benzene sulfonates, olefin-sulfonates and (higher alkyl) sulfates. Among the anionic compounds listed above, preference is given to sodium alkyl alkyl benzene-sulfates having a linear alkyl group (LABS), and in particular to those in which the alkyl group is a straight chain alkyl radical of 12 or 13 carbon atoms.

Non-ionic synthetic organic detergents are characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are produced for example by condensation of an aliphatic or alkyl-aromatic organic hydrophobic compound with ethylene oxide (hydrophilic in nature). Virtually any hydrophobic compound having a carboxy, hydroxy, amido or amino group with a free hydrogen atom attached to nitrogen can be condensed with ethylene oxide or with its polyhydration product, polyethylene glyeol , 'to form a non-ionic detergent. The length of the hydrophilic or polyoxyethylene chain can be easily adjusted to obtain the desired ratio between the hydrophobic and hydrophilic groups.

The nonionic detergent used is preferably a poly (lower alkoxy) higher alkanol group in which the alkanol has 10 to 18 carbon atoms and 16 in which the number of moles of lower alkylene oxide (2 or 3 atoms carbon) is 3 to 12. Among; these materials, it is preferred to use those in which the higher alkanol is a higher fatty alcohol of 11 to 5 15 carbon atoms and which contain 5 to 9 lower alkoxy groups per mole. Preferably, the lower alkoxy is the ethoxy group, but in certain cases, the latter can be advantageously mixed with the pro-poxy group, the latter, if present, generally representing a minor constituent ( less than 50%). Examples of such compounds are those in which the alkanol has 12 to 15 carbon atoms and which contain about 7 ethylene oxide groups per mole, for example Neodol 25-7 and Neodol 23-6.5, which products are fa -15 bricks by Shell Chemical Company, Inc. The first is a condensation product of a mixture of higher fatty alcohols having on average about 12 to 15 carbon atoms, with about 7 moles of ethylene oxide, and the the latter is a corresponding mixture in which the carbon atom content of the higher fatty alcohol is 12 S 13, and the number of ethylene oxide groups per mole is on average about 6.5. Higher alcohols are primary alkanols. Other examples of such detergents include Tergitol® 15-S-7 and Tergitoi - 15-S-9, both of which are linear secondary alcohol ethoxylates manufactured by Union Carbide Corporation. The first is a mixed ethoxylation product of a linear secondary alkanol of 11 to 15 carbon atoms with seven moles of ethylene oxide and the latter is a product a-20 analogous but containing nine moles of oxide d ethylene reacted.

Also useful in the present compositions are higher molecular weight nonionic detergents such as Neodol 45-11, which are condensation products of similar ethylene oxide and higher fatty alcohols, higher fatty alcohol having 14 to 15 to 17 carbon atoms and the number of ethylene oxide groups per mole being about 11. These products are also manufactured by Shell Chemical Company.

Zwitterionic detergents such as betai-5 born and sulfobetanes having the following formula are also useful: R2 10 R—, N - R4- * - ° V -0 formula in which R is an alkyl group having about 8 to 18 atoms of carbon, and R3 each represents an alkyl or hydroxyalkyl group having about 1 to 4 carbon atoms, R ^ is an alkylene or hydroxyalkylene group having 1 to 4 carbon atoms, and X is C or S: 0. The alkyl group may contain one or more intermediate bonds, for example, amido, ether or polyether sounds, or non-functional substituents such as hydroxyl or halogen which do not significantly affect the hydrophobic character of the group.

When X is C, the detergent is called a beta; and when X is S: 0, the detergent is called a sulfo-.

25 betaine or sultaine.

Cationic surfactants can also be used. Ceüx ~ cT include surfactant detergent compounds which contain a hydrophobic organic group forming part of a cation when the com-30 posed is dissolved in water, and an anionic group. Examples of cationic surfactants are the amine and quaternary ammonium compounds.

Examples of suitable synthetic cationic detergents include: primary normal amines of the formula RNHH wherein R is an alkyl group.

* 9 18 both around 12 to 15 carbon atoms; diamines of formula RNHC2H4NH2 in which R is an alkyl group containing approximately 12 to 22 carbon atoms, for example N-2-amino-ethyl-stearyl amine and N-2-aminoethyl-my-5-ristyl-amine; amide-linked amines such as those having the formula R-j CONH2H4NH2 where R-j is an alkyl group having about 8 to 20 carbon atoms, for example N-2-amino-ethylstearyl amide and N-amino-ethyl-myristyl-amide; compounds of the quaternary ammonium type in which, for example, one of the groups linked to the nitrogen atom is an alkyl group containing approximately 8 to 22 carbon atoms and three of the groups linked to the atom nitrogen are alkyl groups which have 1 to 3 carbon atoms, including alkyl groups bearing inert substituents such as phenyl groups, with the presence of an anion such as halogen, acetate, methyl sulfate, etc. . The alkyl group may have intermediate bonds such as amide, which do not significantly affect the hydrophobic character of the group, for example stearyl amido-propyl-quaternary ammonium chloride. Examples of detergents of the quaternary ammonium type are ethyl-dimethyl-stearyl-ammonium chloride, benzyl-dimethyl-stearyl-ammonium chloride,, trimethyl-stearyl ammonium chloride, trimethyl-cetyl-ammonium bromide ,. dimethyl-ethyl-1auryl-ammonium chloride, dimethyl-propyl-myristyl-ammonium chloride and the corresponding methylsulfates and acetates.

Ampholytic detergents are also suitable in the invention. Ampholytic detergents are well known in the art and a large number of usable detergents of this class are described by Schwartz,

Perry and Berch in "Surface Active Agents and Detergents" mentioned above. Examples of suitable amphoteric detergents include the alkyl beta-iminodipropionates RN (C2H4C00M) 2; alkyl (19) RN (H) C2H4C00M alkyl no-propionates; and long chain imidazole derivatives of general formula: CH ~ / Λ 5 N CH2

He I

R-C -N * —CH? CH? 0CH2C00M

/ \

OH CH2C00M

In each of the above formulas, R is an acyclic hydrophobic group containing about 8 to 18 carbon atoms and M is a cation used to neutralize the charge of the anion. Specific amphoteric detergents which can be used include the disodium salt of undecyl-cycloimidinium-ethoxyethionic-2-ethionic acid, dodecyl-beta-alanine and the internal salt of 2-trimethylami-no-lauric acid.

The detergent bleaching compositions of the invention optionally contain a detergency builder salt of the type commonly used in detergent formulations. Useful detergency builders include all conventional mineral water soluble builders, such as water soluble salts such as phosphates, pyrophosphates, orthophosphates, polyphosphates, silicates, carbonates, etc. Organic detergency builders include phosphonates, polyphosphonates, polyhydroxysulfonates, polyacetates, carboxylates, polycarboxylates, succinates, etc., water soluble.

Particular examples of mineral phosphates used as detergency builders include the sodium and potassium tripolyphosphates, pyrophosphates and hexametaphosphates. Organic polyphosphonates include in particular, for example, the sodium and potassium salts of ethane-1-hydroxy-1,1 - 1 - diphosphonic acid and the sodium and potassium salts of ethane acid 1,1,2-triphosphonic. Examples of these as well as other phosphorus compounds used as detergency builders are described in U.S. Patent Nos. 3,213,030; No. 3,422,021; Nos. 3,422,137 and 3,400,176. Pentasodium tripolyphosphate and tetrasodium pyrophosphate are particularly preferred mineral water-soluble detergency builders.

Particular examples of non-phosphorous detergent mineral builders include water-soluble mineral carbonates, bicarbonates and silicates. Particularly preferred here are alkali metal carbonates, bicarbonates and silicates, for example sodium and potassium.

Water-soluble organic detergency builders are also useful. For example, the acetates, carboxylates, polycarboxylates and polyhydrosulfonates of alkali metal, ammonium and substituted ammonium are detergency builders useful for the compositions and methods of the invention. Particular examples of acetates and polycarboxylates serving as detergency builders include the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene-di friendly acid, triacetic acid and triacetic acid. , Benzene-polycarboxylic acids (i.e., pen-ta- and tetra-), carboxymethoxysuccinic acid and citric acid.

It is also possible to use detergency adjuvants which are insoluble in water, in particular complex silicas, and more particularly complex sodium aluminosilicates such as zeolites, for example zeolite 4A, a type of zeolitic molecule in which the monovalent cation is sodium and the pore size is approximately 0.4 nm. The preparation of this type of zeolite is described in US Patent No. ................................. .......... i 21 tallines and present water of hydration as we know in practice.

The use of an inert water-soluble filler salt is advantageous in the bleaching compositions of the invention. A preferred filler salt is an alkali metal sulfate, for example potassium or sodium sulfate, the latter being of particular interest.

Various adjuvants can be incorporated into the laundry detergent compositions of the invention.

In general, these include perfumes; dyes, for example pigments; bleaching agents such as sodium perborate, anti-re-deposition agents, such as the alkali metal salts of carboxymethylcellulose; optical brightening agents, such as anionic, cationic or nonionic brightening agents; foam stabilizers such as al-canolamides, etc., all of which are well known in the art of washing fabrics for use in detergent compositions. Fluidizers commonly referred to as fluidity aids can also be used to maintain the particulate compositions in the form of beads or free flowing powder.

Starch derivatives and special clays are commercially available as additives which improve the flowability of otherwise sticky or pasty particulate compositions, two of these clay-type additives being currently marketed under the trademarks "Satintonè" and "Microsil".

EXAMPLE 1 Thixojel No. 1 agglomerates (a brand of bentonite clay from Wyoming sold by Georgia Kaolin Co., Elizabeth, New Jersey) are used in the present example and prepared by the method The procedure described below in which the following components are used: Thixojel clay No. 1 (0.044 mm) and an aqueous agglomeration solution containing 7% of sodium silicate at a Na ^ OiSiC ^ ratio of approximately 1: 2.4.

The agglomerates are prepared in a rotary drum characterized by a diameter of 50 cm, a length of 60 cm and an axis of rotation adjustable between ten and ninety degrees relative to the vertical.

9.1 kg of Thixojel No. 1 are introduced into the rotary drum described above which is arranged at an angle of 20 degrees with the vertical. 3.2 kg of the aqueous silicate solution is atomized at a temperature of 43 ° C on the clay while rotating the drum at about 6 revolutions / minute. The axis of the rotating drum is then adjusted at an angle of 70 degrees to the vertical and an additional 3.2 kg of silicate solution is sprayed onto the clay. The resulting moist clay agglomerates are transferred in 2 kg portions to an Aeromatic ST-5 (trademark) fluidized bed dryer, manufactured by Aeromatic Corp., Summerville, New Jersey, and dried to a moisture content about 10% by weight using an air flow rate of about 6000 liters per minute and an air inlet temperature of 71 ° C. Drying is carried out for approximately 15 minutes. The dried material is then introduced into a Stokes granulator having a 0.42 mm mesh screen, the particle size of the product being between 0.149 and 0.42 mm. The fines passing through a 0.149 mm mesh screen are recycled to the rotating drum.

A spray-dried granular detergent composition · · is used as a component of the formulations A, B and C described below and having the following composition:

Component Weight percent

Sodium tridecyl benzene sulfonate 15

Sodium tripolyphosphate 33 35 Sodium silicate (1Na20: 2,4Si02) 7 23

Sodium carbonate 5

Borax 2

Sodium sulfate 27.8

Carboxymethyl cellulose 0.2 5 Moisture 10

Formulation A - 100 g of the detergent composition without perfume described above are mixed with 0.2 g of conventional perfume for detergent based on limonene, geraniol, citral, cedrol, benzyl acetate, 10 d pt-butylcyclohexyl acetate and other aromatic ingredients in a Twin-Shell mixer for ten minutes at a mixer speed of about 20 rpm.

Formulation B - 80 g of the detergent composition without perfume described above are mixed with 0.2 g of the same perfume as that used in formulation A according to the procedure described above. 19.8 g of agglomerated Thixogel No. 1 are then added to the mixer, the contents of which are then mixed for approximately 10 minutes at a mixer speed of approximately 20 revolutions / minute.

Formulation C - 19.8 g of Thixojel No. 1 agglomerated are mixed for approximately 10 minutes with 0.2 g of the same perfume as that used in formulations A and B in the twin-envelope mixer mentioned above.

80 g of the above-described unscented detergent composition are then added to the contents of the mixer and mixed for about 10 minutes.

By. Consequently, formulation A represents a conventional detergent formulation containing a perfume; formulation B represents a detergent formulation analogous to A but which, in addition, contains clay agglomerates; and formulation C represents a detergent formulation comprising the support containing the perfume according to the invention.

35 Tests on perfumes are carried out in use.

I ψ 24 sant lots of cotton, Dacron polyester, and a blend (65/35) of Dacron polyester / cotton and terry towels which are washed in a standard US washing machine at 25 ° C using water with a hardness of 100 ppm calculated as calcium carbonate. Each of the three groups of parts described above is washed separately using 100 g of formulations A, B and C, a different formulation being used for each wash.

When the washing process is finished, batches 10 are evaluated and it is found that it is the fabrics washed in formulation C which retain the most perfume odor compared to the fabrics washed with formulations A and B.

On the basis of the above, the use of the sup-port containing the perfume according to the invention in a granular detergent composition allows a large increase in the retention of a perfume on the washed fabrics.

20 1% * *

Claims (22)

25 1. Detergent laundering composition in particles characterized in that it comprises: (a) approximately 0.1 to approximately 50% by weight of a support containing a perfume comprising (i) separate particles containing at least approximately 75% by weight of a mineral clay other than talc and / or a zeolite, and less than approximately 5% by weight of detergent surfactant compounds; and (i i) a perfume; (B) about 2 to about 50% by weight, in addition to any detergent compound contained in said particles, of one or more surfactant detergent compounds selected from anionic, nonionic, cationic, ampholytic and zwitterionic detergents. ; (C) from 0 to about 70% by weight of a detergency builder salt; (d) the remainder consisting of water and optionally a filler salt. 2. A detergent laundering composition in particles according to claim 1, characterized in that the perfume is adsorbed and / or absorbed on the particles. 3. Detergent laundering composition in particles according to claim 1, characterized in that it contains, in addition, a second perfume to reinforce the odor provided by the support containing a perfume. . ___ 4 - detergent laundry composition according to claim 1, characterized in that the detergency builder salt is present in a proportion of about 5 to about 50% by weight. 30 5 - Detergent laundry composition according to claim 1, characterized in that the support particles contain a clay of the smectite type. 6. laundry detergent composition according to claim 5, characterized in that the clay of the type "....................... I 26 7. A laundry detergent composition according to claim 1, characterized in that the weight ratio of the mineral clay and / or the zeolite to the perfume in the support is from about 10: 1 to about 200: 1. 8. A laundry detergent composition according to claim 1, characterized in that the weight of perfume in the support is from about 0.2 to about 10% by weight. 9. A laundry detergent composition according to claim 1, characterized in that the particles contain a zeolite. 10. A laundry detergent composition according to claim 1, characterized in that the particles contain at least 90% by weight of the mineral clay and / or of the zeolite. 11. Method for depositing a perfume on fabrics during laundering, characterized in that the stained and / or soiled fabrics to be washed are brought into contact with an aqueous solution or dispersion containing a support containing a perfume comprising (i ) separate particles containing at least about 75% by weight of a mineral clay other than talc and / or a zeolite and less than about 5 ~% by weight of detergent surfactant compounds; and (iij a perfume; said perfume being adsorbed and / or absorbed on said particles. 12. Method according to claim 11, characterized in that said aqueous solution or dispersion contains a detergent bleaching composition in particles ‘comprising: (a) about 0.1 to about 50% by weight of said support containing a perfume; (b) about 2 to about 50% by weight, in addition to any detergent compound contained in the support, of one or more surfactant detergent compounds chosen from anionic, cationic, nonionic, ampholytic and zwitterionic detergents ; and (c) from 0 to about 70% by weight of a detergency builder salt. • "’ 27 13. The method of claim 11, characterized in that the particles contain a clay of the smectite type. 14. The method of claim 11, charac-5 së in that the clay of the smectite type is a clay of the bentonite type. 15. The method of claim 11, characterized in that the particles contain a zeolite. 16. The method of claim 11, characterized in that the particles contain at least 90% by weight of said mineral clay and / or zeolite. 17. Carrier containing a perfume to be used in admixture with a particular detergent composition or as an additive to a washing solution separate from the detergent composition, characterized in that it comprises (i) separate particles containing at least 75% by weight of a mineral clay other than 1 e talc and / or a zeolite, and less than approximately 5% by weight of detergent surfactant compounds; and (ii) a perfume, which perfume is in the liquid state at room temperature and is adsorbed and / or absorbed on said particles. 18. Support containing a perfume according to claim 17, characterized in that the support particles comprise a clay of the smectite type. 25 19 - Support containing a perfume according to claim 18, characterized in that the clay of the smectite type is bentonite. 20. Support containing a perfume according to claim 17, characterized in that the particles contain * 30 at least 90% by weight of mineral clay and / or of zeoli te. 21. Support containing a perfume according to claim 18, characterized in that the weight ratio of the mineral clay and / or zeolite to the perfume contained in the support is between -about 10: 1 and about 200 : 1. H 28 22. Support containing a perfume according to claim 17, characterized in that the weight of perfume in the support is from approximately 0.2 to approximately 10% by weight. : " AT